U.S. patent application number 17/045494 was filed with the patent office on 2021-06-03 for solid state batteries, sse batteries, lithium metal batteries with solid state electrolytes, hsse, separators, and/or coatings, and/or related methods.
The applicant listed for this patent is Celgard, LLC. Invention is credited to Zhengming Zhang.
Application Number | 20210167420 17/045494 |
Document ID | / |
Family ID | 1000005429259 |
Filed Date | 2021-06-03 |
United States Patent
Application |
20210167420 |
Kind Code |
A1 |
Zhang; Zhengming |
June 3, 2021 |
Solid State Batteries, SSE Batteries, Lithium Metal Batteries with
Solid State Electrolytes, HSSE, Separators, and/or Coatings, and/or
Related Methods
Abstract
The problems or issues faced by typical larger SSE batteries are
solved by providing an interface or interfacial layer at least
between the anode, which comprises Li or Na, and the solid state
electrolyte (SSE). In some other embodiments, an interfacial layer
may be provided between the anode, which comprises Li or Na, and
the SSE, and an interface or interfacial layer may also be provided
between the cathode and the SSE. In at least selected embodiments,
aspects or objects, the interfacial layer may act as a shock
absorber between a SSE (e.g., a sulfide glass SSE) and an anode
material that is soft compared to the SSE (e.g., Li metal). In
other embodiments, the interfacial layer may act as a shock
absorber between the SSE and a cathode material that is softer than
the SSE. In at least certain embodiments, the interfacial layer may
improve ionic conductance between the anode and the SSE and/or the
SSE and the cathode. In at least certain selected embodiments, the
interfacial layer may prevent or deter lithium deposition and
dendrite growth at the interface between the anode and the SSE.
Interface defects at the interface between the anode and the SSE
may allow lithium deposition and dendrite growth. The dendrites may
continue to grow through cracks in the SSE causing a short, which
is a safety issue. The inventive interfacial layer between the
anode and the SSE may prevent or deter this. In at least some
embodiments, the interfacial layer may be a porous polymer layer
filled with liquid electrolyte and may improve ionic conductance
between the anode and the SSE and/or the SSE and the cathode. In
certain embodiments, the anode interface or interfacial layer may
be a porous polymer layer filled with liquid electrolyte. In some
embodiments, the cathode interface or interfacial layer may be a
porous polymer layer filled with liquid, gel or polymer
electrolyte.
Inventors: |
Zhang; Zhengming; (Rock
Hill, SC) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Celgard, LLC |
Charlotte |
NC |
US |
|
|
Family ID: |
1000005429259 |
Appl. No.: |
17/045494 |
Filed: |
April 4, 2019 |
PCT Filed: |
April 4, 2019 |
PCT NO: |
PCT/US2019/025795 |
371 Date: |
October 6, 2020 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
62653603 |
Apr 6, 2018 |
|
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|
Current U.S.
Class: |
1/1 |
Current CPC
Class: |
H01M 2300/0082 20130101;
H01M 10/052 20130101; H01M 4/382 20130101; H01M 4/582 20130101;
H01M 10/0565 20130101; H01M 2300/0094 20130101; H01M 4/366
20130101 |
International
Class: |
H01M 10/0565 20060101
H01M010/0565; H01M 10/052 20060101 H01M010/052; H01M 4/36 20060101
H01M004/36; H01M 4/38 20060101 H01M004/38; H01M 4/58 20060101
H01M004/58 |
Claims
1-109. (canceled)
110. A battery comprises: a lithium metal anode; a cathode; and, a
hybrid solid state electrolyte (HSSE) or interface between the
anode and the cathode including: a cathode interface layer, a solid
state electrolyte (SSE), and an anode interface layer.
111. The battery of claim 110 wherein the cathode interface layer
comprises at least one of the following: nothing, an adhesive,
and/or a polymer skin and/or a film with or without an electrolyte,
and/or a ceramic layer with or without a film base
112. The battery of claim 110 wherein the anode interface layer
comprises at least one of the following: nothing, an adhesive, a
lithium halide, and/or a polymer skin and/or a film with or without
an electrolyte, and/or a ceramic layer with or without a film
base.
113. The battery of claim 110 wherein the hybrid solid state
electrolyte (HSSE) or solid state electrolyte (SSE) comprises an
isotropic and/or elastic Li-ion conductive material.
114. The battery of claim 110 wherein the SSE comprises
polyethylene oxide (PEO).
115. The battery of claim 110 wherein a lithium halide is coated or
deposited onto a surface of the anode, the cathode, the cathode
interface, the anode interface, and/or the SSE.
116. The battery of claim 110 wherein the cathode comprises a
lithium sulfide compound.
117. The battery of claim 116 wherein the lithium sulfide compound
is Li.sub.2S.sub.6.
118. The battery of claim 110 wherein the battery is a new or
improved Li battery, secondary Li battery, SSE battery, solid state
battery, solid state lithium battery, HSSE battery, hybrid
electrolyte battery, multiple electrolyte battery, Li metal
battery, secondary Li metal battery, SSE Li metal battery, solid
state Li metal anode battery, solid state Li metal lithium battery,
HSSE Li metal battery, hybrid electrolyte Li metal battery,
multiple electrolyte li metal battery, and combinations
thereof.
119. In a device, product or vehicle, the improvement comprising
the battery of claim 110.
120. In a SSE battery, the improvement comprising: a solid state
electrolyte (SSE); and a cathode interface layer, an anode
interface layer, or both a cathode interface layer and an anode
interface layer.
121. In a SSE battery, the improvement comprising: a Li metal
anode; a Li Cobalt or Li Sulfur cathode; and, a HSSE including: a
solid state electrolyte (SSE), and a cathode interface layer, an
anode interface layer, or both a cathode interface layer and an
anode interface layer.
121. A Solid State Li battery, comprising: a Li metal anode; a
cathode; and, a HSSE including: a solid state electrolyte (SSE)
layer, and an anode interface layer with liquid, gel or polymer
electrolyte, a cathode interface layer with liquid, gel, or polymer
electrolyte, or both an anode interface layer with liquid, gel or
polymer electrolyte and a cathode interface layer with liquid, gel,
or polymer electrolyte.
122. An improved solid state electrolyte (SSE) battery comprising,
in the following order: a lithium metal or sodium metal containing
anode; a hybrid solid state electrolyte (HSSE); and a cathode,
wherein the HSSE comprises, in the following order: an anode
interface layer, an SSE layer, and an optional cathode interface
layer; an optional anode interface layer, an SSE layer, and a
cathode interface layer; or an anode interface layer, an SSE layer,
and a cathode interface layer, and wherein the cathode interface
layer, when present, is provided on at least one of a surface of
the cathode, a surface of the SSE, or both a surface of the cathode
and a surface of the SSE, and the anode interface layer, when
present, is provided on at least one of a surface of the anode, a
surface of the SSE, or both a surface of the anode and a surface of
the SSE.
123. The battery of claim 122, wherein the lithium-metal-containing
or sodium metal-containing anode is made up of at least one
selected from the group consisting of lithium metal, LiC.sub.6,
Li.sub.22Si.sub.5, Li.sub.15Si.sub.4, Li.sub.22Sn.sub.5, LiAl,
Li.sub.22Pb.sub.5, Li/graphene, Li/Cu, Li/Si, Li/Sn, Li+transition
metal, sodium metal, Na/C.sub.6, or combinations thereof.
124. The battery of claim 122, wherein the cathode is made up of
lithium sulfide, a lithium cobalt based alloy, a lithium iron based
alloy, Li sulfur, Sulfur, Air, NaCoO.sub.2, or O.sub.2.
125. The battery of claim 122, wherein the anode interface layer
has at least one of the following properties: it is softer than the
SSE, it conducts ions, particularly sodium or lithium ions, and it
is electrically insulative.
126. The battery of claim 122, wherein the anode interface layer is
made up of: a lithium halide, including for example, a lithium
iodide, or a sodium halide; a polymer film, layer or membrane with
liquid, gel, or polymer electrolyte therein; and/or a ceramic layer
with a liquid, gel, or polymer electrolyte therein.
127. The battery of claim 122 wherein the SSE layer is at least one
selected from the group consisting of an inorganic glassy or
ceramic SSE, a polymeric SSE, or a combination SSE comprising a
polymer and an inorganic glassy or ceramic material.
128. A hybrid solid state electrolyte (HSSE) comprising, in the
following order: an anode interface layer, a solid state
electrolyte (SSE), and a cathode interface layer; an anode
interface layer and a solid state electrolyte(SSE); or a solid
state electrolyte (SSE) and a cathode interface layer.
129. The HSSE of claim 128, wherein: the anode interface layer is
present and provided directly on a surface of the SSE; or wherein
the anode interface layer and the cathode interface layer are
present, the anode interface layer is provided directly on a
surface of the SSE, and the cathode interface layer is provided
directly on a surface of the SSE opposite to the surface that the
anode interface layer is provided directly on.
130. The HSSE of claim 128, wherein the SSE is at least one
selected from the group consisting of an inorganic glassy or
ceramic SSE, a polymeric SSE, or a hybrid SSE comprising a polymer
and an inorganic glassy or ceramic material.
131. The HSSE of claim 128, wherein the anode interface layer is at
least one selected from the group consisting of: a lithium halide
film, including for example a lithium iodide film, or sodium halide
film; a polymer film with liquid, gel, or polymer electrolyte; a
ceramic layer with a liquid, gel, or polymer electrolyte; a ceramic
coating on a polymer membrane; or a polymer separator with a PVDF
coating or with PVDF in the coating.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a 371 Application which claims priority
to PCT/US2019/025795, filed Apr. 4, 2019, which claims priority to
U.S. Provisional Application Ser. No. 62/653,603, filed Apr. 6,
2018, hereby fully incorporated by reference herein.
FIELD
[0002] In accordance with at least certain inventive embodiments
herein, the problems or issues faced by typical larger SSE
batteries are solved by providing an interface or interfacial layer
at least between the anode, which comprises Li or Na, and the solid
state electrolyte (SSE). In some other embodiments, an interfacial
layer may be provided between the anode, which comprises Li or Na,
and the SSE, and an interface or interfacial layer may also be
provided between the cathode and the SSE. In at least selected
embodiments, aspects or objects, the interfacial layer may act as a
shock absorber between a SSE (e.g., a sulfide glass SSE) and an
anode material that is soft compared to the SSE (e.g., Li metal).
In other embodiments, the interfacial layer may act as a shock
absorber between the SSE and a cathode material that is softer than
the SSE. In at least certain embodiments, the interfacial layer may
improve ionic conductance between the anode and the SSE and/or the
SSE and the cathode. In at least certain selected embodiments, the
interfacial layer may prevent or deter lithium deposition and
dendrite growth at the interface between the anode and the SSE.
Interface defects at the interface between the anode and the SSE
may allow lithium deposition and dendrite growth. The dendrites may
continue to grow through cracks in the SSE causing a short, which
is a safety issue. The inventive interfacial layer between the
anode and the SSE may prevent or deter this. In at least some
embodiments, the interfacial layer may be a porous polymer layer
filled with liquid electrolyte and may improve ionic conductance
between the anode and the SSE and/or the SSE and the cathode. In
certain embodiments, the anode interface or interfacial layer may
be a porous polymer layer filled with liquid electrolyte. In some
embodiments, the cathode interface or interfacial layer may be a
porous polymer layer filled with liquid, gel or polymer
electrolyte. In other embodiments, the anode interface or
interfacial layer may be a porous Li Halide layer. In some
embodiments, the anode interface or interfacial layer may be a
porous Li Halide or Li Iodide layer and the cathode interface or
interfacial layer may be a porous polymer layer filled with liquid,
gel or polymer electrolyte. In still other embodiments, the anode
interface or interfacial layer may be a porous Li Halide or Li
Iodide layer with an optional microporous polymer layer filled with
liquid, gel or polymer electrolyte, and the cathode interface or
interfacial layer may be a microporous polymer layer filled with
liquid, gel or polymer electrolyte. In some possibly preferred
embodiments, the interfacial layer or layers may serve as a shock
absorber (may accommodate changes in volume of one or both
electrodes) and/or may improve ionic conductance between the anode
and the SSE and/or the SSE and the cathode.
BACKGROUND
[0003] Motive power sources (e.g., batteries) are important for the
development of many different devices (for example, handheld
electronic devices, portable computers, other electronic
devices/equipment, hybrid vehicles, and electric vehicles).
[0004] The lithium (Li) battery, particularly the lithium secondary
battery, is a very important battery because it is lightweight and
has a high energy capacity. Such Li batteries generally include: an
intercalated Li graphite as the anode; a lithiated cobalt oxide
(e.g., Li.sub.2CoO.sub.2) as a cathode; liquid electrolyte; and a
microporous polymer membrane as the separator.
[0005] Over the about 30 years of commercial development of the Li
battery (first primary Li batteries, then secondary Li batteries),
the capacity of the Li battery has steadily increased, yet
surprisingly, the best anode, cathode, electrolyte, and separator
materials have remained basically the same, with the exception of
the ceramic coated separator (see U.S. Pat. No. 6,432,586 hereby
fully incorporated by reference) as compared to uncoated polymer
membrane separators. The capacity improvements have been mainly
achieved by reducing inert materials in the Li battery, so that
active materials may be increased. The introduction of the ceramic
coated separator by Zhengm ing (John) Zhang of Celgard, LLC, the
present inventor, allowed separator thickness to be reduced and
energy density to be increased.
[0006] Li solid state electrolyte (SSE) batteries have some known
issues. For example, most of the elastic SSEs may react with a Li
metal anode to form very resistive layers at the interface of the
anode and the SSE. This is illustrated in FIG. 8.
[0007] For crystal or glassy SSEs, even the cathode-SSE interface
can become a problem. With crystal or crystalline SSEs, even more
problems occur, especially if the anode or cathode are made of a
softer material than the crystalline SSEs. The crystalline or
glassy SSEs may damage the anode or cathode material, which is
particularly problematic when the anode is made of soft and
reactive lithium (Li) metal.
[0008] Another issue is potential Li deposition at the interface of
an SSE and lithium metal, which may lead to dendrites and soft or
hard shorts in the battery. An exemplary SSE is shown in FIG.
9.
[0009] Some working small coin cell lithium metal solid state (or
solid-state) batteries have been formed, but not larger high
density electric drive vehicle (EDV) SSE type batteries. Some have
predicted success based on such small coin cell performance, but
successful higher density, larger EDV SSE batteries have not
actually been made. Smaller cells (e.g., coin cells) perform better
than bigger cells because they can much more easily handle changes
in volume of the electrodes during cycling. Also, more conductor or
electrolyte can be added in smaller cells.
SUMMARY
[0010] At least selected embodiments or inventions described herein
may address or solve one or more of the problems or issues
associated with current Li-metal, Na-metal, Li-ion, or Na-ion
primary or secondary batteries having a solid state electrolyte (Li
or Na SSE batteries). A solid state electrolyte (SSE), is
understood by one skilled in the art, as being a solid or glassy
material that moves or conducts Li or Na ions (without liquid
electrolyte). In accordance with at least certain inventive
embodiments herein, the problems or issues faced by typical larger
SSE batteries are solved by providing an interface or interfacial
layer at least between the anode, which comprises Li or Na, and the
solid state electrolyte (SSE). In some other embodiments, an
interfacial layer may be provided between the anode, which
comprises Li or Na, and the SSE, and an interface or interfacial
layer may also be provided between the cathode and the SSE.
[0011] In at least selected embodiments, aspects or objects, the
interfacial layer may act as a shock absorber between a SSE (e.g.,
a sulfide glass SSE) and an anode material that is soft compared to
the SSE (e.g., Li metal). In other embodiments, the interfacial
layer may act as a shock absorber between the SSE and a cathode
material that is softer than the SSE. In at least certain
embodiments, the interfacial layer may improve ionic conductance
between the anode and the SSE and/or the SSE and the cathode. In at
least certain selected embodiments, the interfacial layer may
prevent or deter lithium deposition and dendrite growth at the
interface between the anode and the SSE. Interface defects at the
interface between the anode and the SSE may allow lithium
deposition and dendrite growth. The dendrites may continue to grow
through cracks in the SSE causing a short, which is a safety issue.
The inventive interfacial layer between the anode and the SSE may
prevent or deter this. In at least some embodiments, the
interfacial layer may be a porous polymer layer filled with liquid
electrolyte and may improve ionic conductance between the anode and
the SSE and/or the SSE and the cathode. In certain embodiments, the
anode interface or interfacial layer may be a porous polymer layer
filled with liquid electrolyte. In some embodiments, the cathode
interface or interfacial layer may be a porous polymer layer filled
with liquid, gel or polymer electrolyte. In other embodiments, the
anode interface or interfacial layer may be a porous Li Halide
layer. In some embodiments, the anode interface or interfacial
layer may be a porous Li Halide or Li Iodide layer and the cathode
interface or interfacial layer may be a porous polymer layer filled
with liquid, gel or polymer electrolyte. In still other
embodiments, the anode interface or interfacial layer may be a
porous Li Halide or Li Iodide layer with an optional microporous
polymer layer filled with liquid, gel or polymer electrolyte, and
the cathode interface or interfacial layer may be a microporous
polymer layer filled with liquid, gel or polymer electrolyte. In
some possibly preferred embodiments, the interfacial layer or
layers may serve as a shock absorber (may accommodate changes in
volume of one or both electrodes) and/or may improve ionic
conductance between the anode and the SSE and/or the SSE and the
cathode.
[0012] In at least one possibly preferred aspect or embodiment, an
improved solid state electrolyte (SSE) battery is disclosed. The
SSE battery may include, in the following order: a lithium metal or
sodium metal containing anode; a hybrid solid state electrolyte
(HSSE); and a cathode. The HSSE may include, in the following
order, an anode interface layer, an SSE layer, and an optional
cathode interface layer.
[0013] In some embodiments, the lithium-metal-containing anode is
made up of at least one selected from the group consisting of
lithium metal, LiC.sub.6, Li.sub.22Si.sub.5, Li.sub.15Si.sub.4,
Li.sub.22Sn.sub.5, LiAl, Li.sub.22Pb.sub.5, Li/graphene, Li/Cu,
Li/Si, Li/Sn, Li+ transition metal, or combinations thereof. The
lithium metal or sodium metal containing anode may also be made up
of only lithium metal in some embodiments. In some other
embodiments, the lithium metal or sodium metal containing anode is
made up at least one selected from the group consisting of sodium
metal and Na/C.sub.6. In still other embodiments, the lithium metal
or sodium metal containing anode may be made up of an alloy.
[0014] The cathode of the improved solid state electrolyte battery
(Na or Li SSE Battery) may be made up of lithium sulfide, a lithium
cobalt based alloy, a lithium iron based alloy, Li sulfur, Sulfur,
Air, or O.sub.2. In some embodiments, the cathode is made up of Li
Sulfur (Li--S), Sodium Sulfur (NaS), or NaCoO.sub.2.
[0015] The anode interface layer has, in some possibly preferred
embodiments, at least one of the following properties: it is softer
than the SSE, it conducts ions, particularly sodium or lithium
ions, and it is electrically insulative. In some embodiments, the
anode interface layer has all of the foregoing properties. Examples
of an anode and SSE interface layer in some embodiments include a
layer that is made up of a lithium or sodium halide (e.g., lithium
iodide); a porous or microporous polymer film or membrane with
liquid, gel, or polymer electrolyte; a polymer layer with a liquid,
gel, or polymer electrolyte (such as PEO, PI, PAI, PVDF, or
PVDF:HFP); or a ceramic layer with a liquid, gel, or polymer
electrolyte (with an optional polymer binder, such as PEO, PVDF, or
PVDF:HFP). The anode interface layer may be provided on at least
one of: a surface of the anode, a surface of the SSE, or both a
surface of the SSE and a surface of the anode.
[0016] In the improved SSE battery described in at least certain
embodiments herein, the possibly preferred SSE is at least one
selected from the group consisting of an inorganic glassy or
ceramic SSE, a polymeric SSE, or a combination SSE comprising a
polymer and an inorganic glassy or ceramic material.
[0017] In embodiments where a cathode and SSE interface layer is
present, the cathode interface layer may be provided on at least
one of: a surface of the cathode, a surface of the SSE, or both a
surface of the cathode and a surface of the SSE.
[0018] In another aspect or embodiment, a vehicle, storage system,
or device comprising the improved SSE battery described herein is
provided or described.
[0019] In yet another aspect or embodiment, a hybrid solid state
electrolyte (HSSE) is disclosed herein. The HSSE may be used in the
improved SSE battery described herein. The HSSE may comprise, in
the following order: an anode interface layer, a solid state
electrolyte (SSE) and an optionally provided cathode interface
layer. In some embodiments, the optional cathode interface layer is
present, and in other embodiments it is not.
[0020] In some embodiments, the anode interface layer is provided
directly on a surface of the SSE. Also, in some embodiments where
the optional cathode interface layer is used, it can be provided
directly on a surface of the SSE that is opposite to a surface that
the anode interface is provided on (or provided directly on).
[0021] The SSE of the HSSE described herein may be at least one
selected from the group consisting of an inorganic glassy or
ceramic SSE, a polymeric SSE, or a combination SSE comprising a
polymer and an inorganic glassy or ceramic material.
[0022] The anode interface layer of the HSSE may be at least one
selected from the group consisting of a lithium or sodium halide
film (e.g., a lithium halide film); a porous or microporous polymer
film or membrane with liquid, gel, or polymer electrolyte therein;
a polymer film with liquid, gel, or polymer electrolyte; or a
ceramic layer with a liquid, gel, or polymer electrolyte.
[0023] In another aspect, a new or improved solid state battery
comprising the HSSE described herein above is provided or described
(a HSSE Battery).
[0024] In still another aspect, a vehicle, storage system, or
device comprising the solid-state battery comprising the HSSE
described herein is provided or described.
[0025] In another aspect, a method of making a hybrid solid state
electrolyte (HSSE) is described herein. The method comprises at
least a step of forming an anode interface layer on at least one
side of a solid state electrolyte. Sometimes, the anode interface
layer may be provided directly onto a surface of the SSE and
sometimes it is not. In some embodiments, the method comprises the
additional step of forming a cathode interface layer on a side of
the SSE opposite to the side the anode layer is on or is to be
formed on. Sometimes, the cathode interface layer is formed
directly onto the SSE and sometimes it is not. If the respective
anode and cathode interface layers and the SSE are in cut pieces,
they can be stacked in HSSE production or in cell or battery
production. If the respective anode and cathode interface layers
and the SSE are in roll form, they can be laminated in HSSE
production or in cell or battery production.
[0026] The anode interface layer of the method may be at least one
selected from the group consisting of: a lithium or sodium halide
film (e.g., a lithium iodide film); a polymer film with liquid,
gel, or polymer electrolyte; a porous or microporous polymer film
or membrane with liquid, gel, or polymer electrolyte therein; or a
ceramic layer with a liquid, gel, or polymer electrolyte.
[0027] The SSE of the method may be at least one selected from the
group consisting of an inorganic, glassy, or ceramic SSE, a
polymeric SSE, or a combination SSE comprising a polymer and an
inorganic, glassy, or ceramic material.
[0028] In some preferred embodiments, the SSE is an inorganic,
glassy, or ceramic SSE and the anode interface film is at least one
selected from the group consisting of a lithium or sodium halide
film (e.g., a lithium iodide film); a polymer film with liquid,
gel, or polymer electrolyte; a thin microporous polymer film or
membrane with liquid, gel, or polymer electrolyte therein
(preferably a Celgard.RTM. dry process polyolefin microporous
polymer film or membrane with a liquid electrolyte for good or
improved ionic conduction, good or improved resilience, and good or
improved dendrite prevention); or a ceramic layer with a liquid,
gel, or polymer electrolyte.
[0029] In another aspect, a method for making an improved solid
state battery is described herein. The method comprises at least a
step of forming an anode interface layer on at least one of the
following: a side of a solid state electrolyte (SSE); a side of an
anode that will be facing the SSE in the solid state battery; and
both a side of an SSE and a side of an anode, wherein the side of
the SSE and the side of the anode are facing each other in the
solid state battery. In some embodiments, the anode interface layer
is formed directly on the anode or directly on the SSE.
[0030] In another aspect, a method for making an improved solid
state battery is described herein. The method comprises at least a
step of forming a cathode interface layer on at least one of the
following: a side of a solid state electrolyte (SSE); a side of a
cathode that will be facing the SSE in the solid state battery; and
both a side of an SSE and a side of a cathode, wherein the side of
the SSE and the side of the cathode are facing each other in the
solid state battery. In some embodiments, the cathode interface
layer is formed directly on the cathode or directly on the SSE.
[0031] In another aspect, a method for making an improved solid
state battery is described herein. The method comprises a step of
forming an anode interface layer, and an additional step of forming
a cathode interface layer is included in the method for making an
improved solid state battery. In such embodiments, a cathode
interface layer is formed on at least one of the following: a side
of the SSE that is opposite to the side of the SSE that the anode
interface layer is or will be formed on; a side of cathode that
will be facing the SSE in the solid state battery, and both the
side of the SSE that is opposite to the side of the SSE that the
anode interface layer is or will be formed on and on the side of
the cathode that will be facing the SSE in the solid state battery.
In some embodiments, the cathode interface layer is formed directly
on the SSE or directly on the cathode.
[0032] The anode interface layer used in this method may be at
least one selected from the group consisting of: a lithium or
sodium halide film (e.g., lithium iodide), a polymer film with
liquid, gel, or polymer electrolyte, a porous or microporous
polymer film or membrane with liquid, gel, or polymer electrolyte
therein (preferably a Celgard.RTM. dry process polyolefin
microporous polymer film or membrane with a liquid electrolyte for
good or improved ionic conduction, good or improved resilience, and
good or improved dendrite prevention), and a ceramic layer with a
liquid, gel, or polymer electrolyte.
[0033] The SSE used in this method may be, in some embodiments, at
least one selected from the group consisting of an inorganic,
glassy, or ceramic SSE, a polymeric SSE, or a combination SSE
comprising a polymer and an inorganic, glassy, or ceramic
material.
[0034] In some preferred embodiments, the SSE is an inorganic,
glassy, or ceramic SSE and the anode interface layer is at least
one selected from the group consisting of: a lithium or sodium
halide film (e.g., lithium iodide), a polymer film or layer with
liquid, gel, or polymer electrolyte, a porous or microporous
polymer film or membrane with liquid, gel, or polymer electrolyte
therein (preferably a Celgard.RTM. dry process polyolefin
microporous polymer film or membrane with a liquid electrolyte for
good or improved ionic conduction, good or improved resilience, and
good or improved dendrite prevention), and a ceramic layer with a
liquid, gel, or polymer electrolyte.
[0035] In some other preferred embodiments, the SSE is an
inorganic, glassy, or ceramic SSE and the cathode interface layer
is at least one selected from the group consisting of: a lithium or
sodium halide film (e.g., lithium iodide), a polymer film or layer
with liquid, gel, or polymer electrolyte, a porous or microporous
polymer film or membrane with liquid, gel, or polymer electrolyte
therein (preferably a Celgard.RTM. dry process polyolefin
microporous polymer film or membrane with a liquid electrolyte for
good or improved ionic conduction, good or improved resilience, and
good or improved dendrite prevention), and a ceramic layer with a
liquid, gel, or polymer electrolyte.
[0036] In still other preferred embodiments, the SSE is an
inorganic, glassy, or ceramic SSE and the anode and cathode
interface layers are each at least one selected from the group
consisting of: a lithium or sodium halide film (e.g., lithium
iodide), a polymer film or layer with liquid, gel, or polymer
electrolyte, a porous or microporous polymer film or membrane with
liquid, gel, or polymer electrolyte therein (preferably a
Celgard.RTM. dry process polyolefin microporous polymer film or
membrane with a liquid electrolyte for good or improved ionic
conduction, good or improved resilience, and good or improved
dendrite prevention), and a ceramic layer with a liquid, gel, or
polymer electrolyte.
[0037] In a possibly more preferred embodiment, the SSE is an
inorganic, glassy, or ceramic SSE and the anode interface layer is
or layers are each at least one selected from the group consisting
of: a lithium or sodium halide film (e.g., lithium iodide), and a
porous or microporous polymer film or membrane with liquid, gel, or
polymer electrolyte therein (preferably a Celgard.RTM. dry process
polyolefin microporous polymer film or membrane with a liquid
electrolyte for good or improved ionic conduction, good or improved
resilience, and good or improved dendrite prevention).
[0038] In a possibly more preferred embodiment, the SSE is an
inorganic, glassy, or ceramic SSE and the anode interface layer and
an optional cathode interface layer are each at least one selected
from the group consisting of: a lithium or sodium halide film
(e.g., lithium iodide), and a porous or microporous polymer film or
membrane with liquid, gel, or polymer electrolyte therein
(preferably a Celgard.RTM. dry process polyolefin microporous
polymer film or membrane with a liquid electrolyte for good or
improved ionic conduction, good or improved resilience, and good or
improved dendrite prevention).
[0039] In a possibly preferred embodiment, the SSE is an inorganic,
glassy, or ceramic SSE and the anode and/or cathode interface
layers are each at least one selected from the group consisting of:
a porous or microporous polymer film or membrane with liquid, gel,
or polymer electrolyte therein (preferably a Celgard.RTM. dry
process polyolefin microporous polymer film or membrane with a
liquid electrolyte for good or improved ionic conduction, good or
improved resilience, and good or improved dendrite prevention), and
a ceramic or polymer layer with a liquid, gel, or polymer
electrolyte.
[0040] Accordingly, the following new or improved batteries are
proposed:
[0041] Accordingly, the following new or improved Li Metal Battery
is proposed:
[0042] A battery comprises: [0043] a lithium metal anode; [0044] a
cathode; and, [0045] a hybrid solid state electrolyte (HSSE)
between the anode and the cathode including: [0046] a cathode
interface layer, [0047] a solid state electrolyte (SSE) layer, and
[0048] an anode interface layer. [0049] These elements are
described in greater detail below.
[0050] Accordingly, the following new or improved Li Metal Solid
State Battery is proposed:
[0051] A battery comprises: [0052] a lithium metal anode; [0053] a
cathode; and, [0054] a hybrid solid state electrolyte (HSSE)
between the anode and the cathode including: [0055] a cathode
interface layer, [0056] a solid state electrolyte (SSE), and [0057]
an anode interface layer. [0058] These elements are described in
greater detail below.
[0059] Accordingly, the following new or improved Solid State
Battery is proposed:
[0060] A battery comprises: [0061] an anode, such as a lithium
metal or sodium metal anode, preferably a lithium metal anode;
[0062] a cathode, such as a Li Sulfur, sodium sulfur, or Li Cobalt
cathode; and, [0063] a hybrid solid state electrolyte (HSSE)
between the anode and the cathode including: [0064] an optional
cathode interface layer, [0065] a solid state electrolyte (SSE),
and [0066] an optional anode interface layer. [0067] These elements
are described in greater detail below.
[0068] Accordingly, the following new or improved Solid State
Battery is proposed:
[0069] A battery comprises: [0070] an anode, preferably a lithium
metal anode; [0071] a cathode, such as a Li Sulfur, sodium sulfur,
or Li Cobalt cathode; and, [0072] a hybrid solid state electrolyte
(HSSE) between the anode and the cathode including: [0073] an
optional cathode interface layer, [0074] a solid state electrolyte
(SSE), and [0075] an anode interface layer. [0076] These elements
are described in greater detail below.
[0077] Accordingly, the following new or improved Solid State
Battery is proposed:
[0078] A battery comprises: [0079] an anode, preferably a lithium
metal anode; [0080] a cathode, such as a Li Sulfur, sodium sulfur,
or Li Cobalt cathode; and, [0081] a hybrid solid state electrolyte
(HSSE) between the anode and the cathode including: [0082] a
cathode interface layer, [0083] a solid state electrolyte (SSE),
and [0084] an optional anode interface layer. [0085] These elements
are described in greater detail below.
[0086] The use of Li metal for the anode in the lithium or solid
state Li battery is one preferred alternative. The use of Li metal
is not new, but Li metal is not used because of the historical
issues and concerns about its use.
[0087] The use of a Li Sulfur cathode in the battery is one
preferred alternative. The removal of cobalt from the cathode would
be a welcome improvement because the price of cobalt is currently
on the increase due to demand and because Sulfur provides higher
energy.
[0088] Accordingly, the following new battery options are
proposed:
[0089] A battery comprises: [0090] an anode, preferably a lithium
metal anode; [0091] a cathode, preferably a Li Cobalt or Li Sulfur
cathode; and, [0092] a hybrid solid state electrolyte (HSSE)
between the anode and the cathode including: [0093] an optional
cathode interface layer or layers, [0094] a solid state electrolyte
(SSE), and [0095] an optional anode interface layer or layers.
DETAILED DESCRIPTION
[0096] Embodiments described herein can be understood more readily
by reference to the following detailed description, examples, and
figures. Elements, apparatus, and methods described herein,
however, are not limited to the specific embodiments presented in
the detailed description, examples, and figures. It should be
recognized that these embodiments are merely illustrative of the
principles of the present invention. Numerous modifications and
adaptations will be readily apparent to those of skill in the art
without departing from the spirit and scope of the invention.
[0097] In addition, all ranges disclosed herein are to be
understood to encompass any and all subranges subsumed therein. For
example, a stated range of "1.0 to 10.0" should be considered to
include any and all subranges beginning with a minimum value of 1.0
or more and ending with a maximum value of 10.0 or less, e.g., 1.0
to 5.3, or 4.7 to 10.0, or 3.6 to 7.9.
[0098] All ranges disclosed herein are also to be considered to
include the end points of the range, unless expressly stated
otherwise. For example, a range of "between 5 and 10," "from 5 to
10," or "5-10" should generally be considered to include the end
points 5 and 10.
[0099] Further, when the phrase "up to" is used in connection with
an amount or quantity, it is to be understood that the amount is at
least a detectable amount or quantity. For example, a material
present in an amount "up to" a specified amount can be present from
a detectable amount and up to and including the specified
amount.
[0100] Disclosed herein is an improved solid state electrolyte
(SSE) battery (such as a lithium or sodium SSE battery) comprising
a hybrid solid state electrolyte (HSSE), the HSSE itself, vehicles,
storage systems, and devices comprising the improved solid state
electrolyte battery and the HSSE, batteries comprising the HSSE,
methods for manufacturing the HSSE, and methods for manufacturing
the improved solid state electrolyte battery comprising the
HSSE.
[0101] Some aims of this disclosure are to address past issues with
solid state batteries and/or SSEs, to protect the SSE, anode,
and/or cathode, to provide a practical, long cycle life, and/or
constant charge battery, such as a Li metal battery, Li metal solid
state battery, SSE battery, or HSSE battery, and/or to provide a
novel or improved anode, SSE, anode+SSE, modified anode, anode+Li
Iodide layer, SSE+Li Iodide layer, HSSE, and/or the like, and/or
combinations thereof, and it may be beneficial to include: an ion
conductive cathode interface layer and/or an ion conductive anode
interface layer between the SSE and the appropriate electrode(s),
to protect the SSE, anode, and/or cathode, to enhance ion
conductivity, to prevent or inhibit dendrite growth, to improve
battery safety, and combinations thereof. In general, the interface
layer may be at least one of the following: nothing (i.e., the SSE
is in direct contact with one or both the electrodes); and/or a
polymer skin (e.g., a coating) or film (such as a polyolefin (PO)
membrane or layer) with or without a liquid, gel or polymer
electrolyte; and/or a ceramic layer with or without a film base.
The coating or film (including the film base) may be a polymer
based material. Such polymers include, for example, polyolefins
(e.g., PE, PP), polyamdies (e.g., nylons), or polyesters (e.g.,
PET). The polymer skin and film (including the film base) may be
nonporous, porous, or microporous. The electrolyte may be
impregnated throughout the polymer skin or film (including the film
base). In one embodiment the ceramic may include aluminum oxide
(Al.sub.2O.sub.3), Li Iodide, a Li Halide, and/or the like. The
interface layer may be applied to either the SSE and/or the
electrode in any conventional manner (depending upon the nature of
the SSE and the interface layer, including, for example, stacking,
lamination, coating, or vapor deposition to name a few).
[0102] Additionally, a lithium halide may be coated on a surface of
one or both of the electrodes, the SSE, the HSSE, and/or
combinations thereof. In one embodiment, the lithium halide is
preferably lithium iodide (LiI).
Solid-State Electrolyte (SSE) Battery
[0103] The solid-state electrolyte battery described herein is not
so limited and may comprise, consist of, or consist essentially of,
in the following order, an anode, a hybrid solid state electrolyte
(HSSE) as described herein, and a cathode. In some embodiments, the
solid-state electrolyte battery described herein may comprise,
consist of, or consist essentially of, in the following order, a
current collector, an anode, an HSSE (optionally preferably with
liquid, gel or polymer electrolyte in one or more interface
layers), a cathode, and a current collector. Further the
solid-state electrolyte battery may comprise, consist of, or
consist essentially of the foregoing components and any additional
components. The solid state electrolyte battery may be a
cylindrical battery or cell, a coin battery or cell, a button
battery or cell, a prismatic battery or cell, a stacked battery or
cell, or a pouch battery or cell. In some preferred embodiments,
the solid state electrolyte battery may be a large or big format
cell, i.e., not a button battery or cell or a coin battery or cell.
Some effective small format lithium metal batteries have been
created, but formation of safe and stable large format cells (such
as EDV, ESS, or the like) has been elusive.
[0104] A battery according to some embodiments, described herein is
shown in the FIG. 1.
[0105] A battery according to some other embodiments described
herein is shown in FIG. 2.
[0106] A battery according to some other embodiments described
herein is shown in FIG. 3.
[0107] A battery according to some other embodiments described
herein is shown in FIG. 4.
[0108] A battery according to some other embodiments described
herein is shown in FIG. 5.
Anode
[0109] The anode described herein is not so limited and may be made
of any material known to be or later found to be acceptable for use
as an anode material. In some preferred embodiments described
herein, the anode may be made of a lithium-metal-containing or
sodium-metal-containing material. The anode may comprise, consist
of, or consist essentially of the lithium-metal-containing or
sodium-metal-containing material. The lithium-metal-containing
material may be lithium metal by itself or any alloy comprising
lithium. Lithium metal refers to Li metal and not intercalated
compound anodes. Examples of alloys comprising lithium include, but
are not limited to, LiC.sub.6, Li.sub.22Si.sub.5,
Li.sub.15Si.sub.4, Li.sub.22Sn.sub.5, LiAl, Li.sub.22Pb.sub.5,
Li/graphene, Li/Cu, Li/Si, Li/Sn, and Li+transition metal. The
anode may also comprise, consist of, or consist essentially of a
mixture of lithium metal alloys or a mixture of lithium metal with
one or more lithium metal alloys. The sodium-containing-metal
material may be sodium itself or an alloy comprising sodium. An
example of an alloy comprising sodium includes, but is not limited
to, Na/C.sub.6. The anode may comprise, consist of, or consist
essentially of sodium metal itself, a combination of sodium metal
and one or more sodium containing alloys, a sodium containing alloy
itself, or a mixture of two or more sodium-containing alloys.
[0110] In some other preferred embodiments, the anode is made up of
or comprises, consists of, or consists essentially of a soft
material. The term "soft material" here is understood to mean a
material as soft as or softer than lithium metal or sodium metal. A
soft material is one that may be damaged by a solid state
electrolyte, particularly an inorganic, glassy or ceramic SSE, when
placed in direct contact with the soft anode in a typical
solid-state electrolyte battery that does not comprise the anode
interface layer or layers described herein. Lithium metal and other
materials that are as soft as lithium or softer can be damaged by
interaction with an SSE in a typical SSE battery. This damage may
include removal of pieces of the anode by the SSE, and due to the
reactive nature of lithium, this can be dangerous. Smaller pieces
of lithium metal means increased surface area on which a reaction
can occur. Other soft alkali metals are reactive like lithium.
[0111] Other possible anode alloys are disclosed below:
TABLE-US-00001 Alloy (Expansion) mAH/g mAH/cm3 Li (+100%) 3860 2060
LiC.sub.6 (+10%) 370 800 All Below are Nano-Structure Composites
with C or other Li.sub.22Si.sub.5 (+300%) 4200 10,000
Li.sub.15Si.sub.4 3580 8300 Li.sub.22Sn.sub.5 (+360%) 990 7200 LiAl
990 2700 Li.sub.22Pb.sub.5 570 6500 Li/Graphene vs. Li/Cu? Huge
number of nucleation sites = low current density Li/Si or Li/Sn +
Graphene? Li = nano-Transition Metal, e.g., Co = Carbon
[0112] Cathode
[0113] The cathode described herein is also not limited. It may be
made of any material known or later found to be an acceptable
cathode material. In some embodiments, the cathode may comprise,
consist of, or consist essentially of lithium sulfide, a lithium
cobalt based alloy, a lithium iron based alloy, Li sulfur, Na
Sulfur, Sulfur, Air, O.sub.2, or combinations thereof.
[0114] The cathode may be any cathode material. In one embodiment,
the cathode material may be a lithium cobalt-based cathode active
materials (such as NCA, CSG, LMO, LFP, LCO, NMC). In one preferred
embodiment, the cathode material may be a lithium sulfur or sulfide
system (including or not including cobalt). In another embodiment,
the lithium sulfide system may comprise Li.sub.2S.sub.6.
[0115] Some Lithium and Sodium Anode and Cathode Systems are
disclosed below:
TABLE-US-00002 ENERGY DENSITY WH/L:WH/Kg WH/L:WH/Kg ANODE CATHODE
THEORETICAL APPLICATION PbAc/NiCd/NiMeH 160/1000 100/450 60/300
35/150 Li/C.sub.6 LiCoO.sub.2 1800 580 700 300 Li/C.sub.6
LiFePO.sub.4 1540 540 220 120 Li/Si LiCoO.sub.2 1800 580 730
250(350) Li Sulfur 2600 2500 320 350 Li O.sub.2 8000 11,000 .sup.
600.sup.x .sup. 800.sup.x Na/C.sub.6 NaCoO.sub.2 1400 500 <Li
Ion ~Same Gasoline O.sub.2 9000 13,000 1800.sup.y 2600.sup.y
(C.sub.8H.sub.18) .sup.xPolyPlus Li-Encapsulation for Lithium/Air
Anode .sup.y20% Carnot efficiency
[0116] Hybrid Solid-State Electrolyte
[0117] The hybrid solid state electrolyte (HSSE) described herein
is not so limited. The HSSE, in some preferred embodiments, may
comprise, consist of, or consist essentially of an anode interface
layer and a solid state electrolyte (SSE) layer in that order. The
HSSE, in other embodiments, may comprise, consist of, or consist
essentially of a solid state electrolyte (SSE) layer and a cathode
interface layer in that order. In other embodiments, the HSSE may
comprise, consist of, or consist essentially of an anode interface
layer, an SSE layer, and a cathode interface layer, in that order.
In a battery, the anode interface layer is positioned between the
anode and the SSE and the cathode interface layer is positioned
between the cathode and the SSE.
[0118] Some functions that may be served by the hybrid solid state
electrolyte (HSSE) include the function of a hybrid or composite
separator between the anode and the cathode. For example, the HSSE
allows for ionic conduction and transport (e.g., of lithium ions)
while providing physical separation of the electrodes. In some
embodiments, the HSSE may also prevent electrical shorting by
blocking, eliminating, preventing, and/or reducing the growth of
dendrites. Dendrite growth normally occurs during battery cycling.
The HSSE structure may also, in some embodiments, protect the
anode, cathode, or both from damage by the SSE, particularly an SSE
that is harder than the anode or the cathode. In some embodiments,
the HSSE should have a smooth and/or malleable (or elastic) face,
at least adjacent, abutting, or contacting the anode, especially a
smooth Li metal anode, so that good surface contact (facilitating
ion conduction) may be maintained with the electrodes as the
electrodes expand and contract during battery cycling (volume
change due to Li movement). The HSSE should be stable (e.g.,
chemically stable) in the battery environment. The HSSE should not
react with the electrodes.
[0119] An HSSE according to some embodiments herein is shown in
FIG. 6.
[0120] Solid State Electrolyte
[0121] The solid state electrolyte (SSE) is not so limited and may
be made up of any material known or found to be acceptable for the
formation of a solid state electrolyte. Particularly, the solid
state electrolyte may be made up of a material known or discovered
to be an acceptable solid state electrolyte for a lithium metal,
lithium ion, sodium metal, or sodium ion primary or secondary
battery.
[0122] In some preferred embodiments, the solid state electrolyte
may be a polymeric SSE. For example, the polymeric SSE may be any
one described in the article Agrawal et al., Solid Polymer
Electrolytes Materials Designing and All Solid-State Battery
Applications: An Overview, Journal of Physics D. Applied Physics,
October 2008, which is incorporated herein by reference in its
entirety. As described in the Agrawal et al. article, the polymeric
SSE may be a conventional polymer--salt complex or dry solid
polymeric electrolyte (SPE), a plasticized polymer--salt complex, a
polymer gel electrolyte, a rubbery polymer electrolyte, or a
composite polymer electrolyte which comprises micro or nanosize
inorganic (ceramic)/organic filler particles dispersed into a
conventional SPE host. Solid polymeric electrolytes are also
disclosed in Sun et al., Recent Advances in All-Solid-State
Rechargable Lithium Batteries, Nano Energy 33(2017)363-386 which is
incorporated herein by reference in its entirety.
[0123] Polymeric electrolytes are known to have a problem of having
low ionic conductivity at room temperature, which is necessary to
produce a marketable battery that will be used at these
temperatures. However polymeric electrolyte are generally preferred
when it comes to flexibility and safety.
[0124] In accordance to some embodiments described herein, the
interface layers may help to improve the ionic conductivity of
polymeric solid state electrolytes or SPE. In some other
embodiments, the interface layers (particularly the anode interface
layers) described herein may improve the polymeric solid state
electrolytes ability to block, eliminate, prevent, and/or reduce
the growth of dendrites.
[0125] In some other preferred embodiments, the solid state
electrolyte is an inorganic, glassy, or ceramic solid state
electrolyte. Some examples of inorganic, glassy, or ceramic solid
state electrolytes are described in the article Sun et al., Recent
Advances in All-Solid-State Rechargable Lithium Batteries, Nano
Energy 33(2017)363-386 which is incorporated herein by reference in
its entirety. Some examples of materials of inorganic, glass, or
ceramic solid state electrolytes include Li3N, LiPON, Li2S-based
glass, NaSICON-type oxides, Li0.05-3xLa0.5+xTiO3, and
Li7La3Zr2O12.
[0126] Generally, inorganic, glassy, or ceramic solid state
electrolytes provide better ionic conductivity than polymeric solid
state electrolytes do and may better block the passage of
dendrites. However, these glassy or crystalline SSEs are also more
rigid or less flexible than polymeric solid state electrolytes.
There is a known problem with inorganic, glassy, or ceramic solid
state electrolytes, particularly when used with softer anode or
cathode materials, that the inorganic, glassy, or ceramic SSE will
damage the anode or cathode materials causing safety issues. In
some other embodiments, the interface layers described herein may
improve the safety of batteries formed using soft anode or cathode
materials (e.g., lithium metal) with an inorganic, glassy, or
ceramic SSE.
[0127] In some other preferred embodiments, the SSE is a
combination SSE comprising polymer material and an inorganic,
glassy, or ceramic material. Exemplary materials are disclosed in
Sun et al., Recent Advances in All-Solid-State Rechargable Lithium
Batteries, Nano Energy 33(2017)363-386 and Agrawal et al., Solid
Polymer Electrolytes Materials Designing and All Solid-State
Battery Applications: An Overview, Journal of Physics D. Applied
Physics, October 2008. In some other embodiments, the inventive
interface layers (particularly the anode interface layers)
described herein may improve the polymeric solid state electrolytes
ability to block, eliminate, prevent, and/or reduce the growth of
dendrites.
[0128] Combination SSEs have better conductivity generally than
polymeric SSEs, but still lower conductivity than some inorganic,
glassy, or ceramic SSEs. The combination SSEs however, are less
rigid generally than inorganic, glassy, or ceramic SSEs. In some
embodiments, the interface layers described herein may improve the
safety of batteries formed using soft anode or cathode materials
(e.g., lithium metal) with a combination SSE. In some other
embodiments, the interface layers may improve the conductivity of
the combination SSE particularly at the interface of the SSE and
the anode or the interface of the SSE and the cathode. In some
other embodiments, the interface layers (particularly the anode
interface layers) described herein may improve the polymeric solid
state electrolytes ability to block, eliminate, prevent, and/or
reduce the growth of dendrites.
[0129] In some embodiments a highly elastic SSE like a sulfide
glass (super-cooled liquid) is preferred as the SSE. In other
preferred embodiments, the preferred SSE is an isotropic SSE (with
3 dimensional conductivity). In other embodiments, the preferred
SSE is an isotropic, strong, and elastic SSE.
[0130] Some other SSEs acceptable for use herein are found in the
Table (FIG. 10), which is From Kerman et al. JES 167(7)
A1731-A174A(2017), which is incorporated herein in its
entirety.
[0131] In other embodiments, the SSE may be any material, but is,
in some embodiments, preferably not a polymer or gel electrolyte
(as understood by those of ordinary skill , see, for example,
Wikipedia--Electrolyte/solid electrolyte, Linden (ed), Handbook of
Batteries, 2.sup.nd edition, McGraw-Hill, Inc. 1995, page 36.20 et
seq; Besenhard (editor), Handbook of Battery Materials, Wiley-VCH,
1999, pages 557 et seq.; Arora/Zhang, Battery Separators, Chem.
Rev, 104, pages 4441-4442; Zhang, S, A Review of the Separators of
Liquid Electrolyte Li-ion Batteries, J. Power Sources 164 (2007)
page 361). The SSE may be a dry electrolyte (or a dry polymer
electrolyte) and/or a solid ceramic electrolyte and/or an organic
ionic plastic crystal. Such dry electrolytes usually have high
dielectric constants. The dry electrolyte may include, for example:
polyethylene oxide (PEO), poly methylmethacrylate (PMMA),
polyphosphazenes, and siloxanes. In one preferred embodiment, the
dry electrolyte may be PEO. The solid ceramic electrolytes (or
glassy-ceramic electrolytes) allow ions to migrate through the
ceramic phase by means of vacancies or interstitial spaces or voids
within the lattice. Organic ionic plastic crystals may be a type of
organic salts exhibiting mesophases (i.e., a state of matter
intermediate between liquid and solid), in which mobile ions are
orientationally or rotationally disordered while their centers are
located at the ordered sites in the crystal structure. These
crystals have various forms of disorder due to one or more
solid--solid phase transitions below the melting point and have,
therefore, plastic properties and good mechanical flexibility as
well as improved electrode|electrolyte interfacial contact. In
particular, protic organic ionic plastic crystals (POIPCs), which
are solid protic organic salts formed by proton transfer from a
Bronsted acid to a Bronsted base and in essence are protic ionic
liquids in the molten state. Examples of these crystals may include
1,2,4-triazolium perfluorobutanesulfonate and imidazolium
methanesulfonate.
[0132] Anode Interface Layer
[0133] The anode interface layer described herein is not so
limited. In some embodiments, the anode interface layer may address
some of the above mentioned problems with traditional SSEs,
including the low ionic conductivity of polymeric SSEs and the
hardness of inorganic, glassy, or ceramic SSEs, which can damage a
soft anode material like lithium metal or sodium metal.
[0134] In some embodiments, the anode interface layer has at least
some of the following properties: low resistance, can act as shock
absorber, ionically conductive, electrically insulative, is softer
than the SSE, etc.
[0135] In some embodiments, the anode interface layer may be at
least one selected from the group consisting of the following:
lithium or sodium halide film; a porous polymer film or membrane
with liquid, gel, or polymer electrolyte; a ceramic layer with a
liquid, gel, or polymer electrolyte; a polymeric film without a
liquid, gel, or polymer electrolyte; and combinations thereof. In
some embodiments, the interface layer may comprise two or more
layers, for example, a polymer film (or base film) without an
electrolyte and a ceramic layer with a liquid, gel or polymer
electrolyte.
[0136] In some embodiments, the anode interface layer is formed
onto at least one of a surface of an anode, a surface of an SSE, or
both a surface of an anode and a surface of an SSE. In some
embodiments, the anode interface layer may be formed directly on a
surface of the anode or SSE, and in other embodiments, there may be
one or more intervening layers formed in between the anode or SSE
surface and the anode interface layer. Regardless of how the
interface layer is formed, in the resulting battery, the anode
interface layer is between the anode and the SSE.
[0137] In some embodiments, the anode interface layer may be a film
or comprise at least one film that comprises, consists of, or
consists essentially of a lithium or sodium halide. For example, in
some preferred embodiments, the anode interface layer may be a film
or comprise at least one film that comprises, consists of, or
consists essentially of lithium halide (like lithium iodide).
Lithium halide is a preferred material because it is both ionically
conductive and electrically insulative. Thus, the anode interface
layer may be a film or comprise at least one film that comprises,
consists of, or consists essentially of any material that is both
ionically conductive (e.g., for lithium ions) and electrically
insulative like lithium iodide is regardless of whether the
material is a sodium or lithium halide.
[0138] In some preferred embodiments, an anode interface layer that
includes a lithium or sodium halide is paired with an inorganic,
glassy, or ceramic SSE in the HSSE described herein. The lithium or
sodium halide--containing anode interface layer may act as a shock
absorber to prevent damage of a soft anode material (e.g., lithium)
by the inorganic, glassy, or ceramic SSE.
[0139] In some embodiments, the anode interface layer is or
includes a polymer film. In some embodiments, the polymer film is
nonporous, porous, microporous, macroporous, or nanoporous. In
embodiments where the polymer film is nonporous, the film
preferably is ionically conductive. For example, the polymer film
may be made of, comprise, consist of or consist essentially of PVDF
polymer or PVDF:HFP copolymer. In other preferred embodiments, the
polymer film is microporous and made up of polymers such as
polyolefins (e.g., PE, PP), polyamdies (e.g., nylons), or
polyesters (e.g., PET), and combinations thereof. In some preferred
embodiments, the polymer film is a Celgard.RTM. dry process
polyolefin film or membrane manufactured by Celgard, LLC of
Charlotte, N.C., especially a polypropylene (PP) film or a
multilayer PP and/or PE film, with good compression and rebound
(good resilience over many cycles).
[0140] In some more preferred embodiments, an anode interface layer
that includes a polymer film as described herein is paired with an
inorganic, glassy, or ceramic SSE in the HSSE described herein. The
polymer-film-containing interface layer may also act as a shock
absorber to prevent damage of a soft anode material (e.g., lithium)
by the inorganic, glassy, or ceramic SSE, act as an electrolyte
reservoir and improve conductance, improve safety by protecting
soft anodes, or combinations thereof. The polymer-film-containing
interface layer may also reduce, prevent, or block dendrites.
[0141] In other embodiments, the anode interface layer is or
includes a polymer film as described herein with a liquid, gel, or
polymer electrolyte. The electrolyte may be coated on or soaked or
impregnated into the polymer film. In embodiments where the polymer
film is porous, the electrolyte may fill, coat, or both fill and
coat the pores.
[0142] In some embodiments, use of a polymer film with a polymer,
gel, or liquid electrolyte is preferred when the SSE has lower
ionic conductivity as the electrolyte will improve ionic
conductivity.
[0143] In some other preferred embodiments, the anode interface
layer comprises or is a ceramic layer. The ceramic layer may
comprise, consist of, or consist essentially of micro- or
nano-sized particles dispersed in a binder. The particles may be
heat resistant particles and the binder may be a polymeric
binder.
[0144] In some embodiments the ceramic layer may be used alone as
the anode interface layer and in other embodiments the ceramic
layer may be coated with or soaked in or impregnated with solid,
gel, or polymer electrolyte. In other embodiments, the ceramic
layer may be coated on a polymer film as described herein and in
other embodiments the ceramic coated polymer film may be soaked in
or impregnated with or coated with electrolyte and this electrolyte
filled composite can be used as the anode interface layer.
[0145] In some embodiments, the use of a ceramic layer, with or
without a polymeric film and with or without electrolyte, as the
interface layer may also reduce, prevent, or block dendrites. In
some embodiments, addition of electrolyte improves ionic
conductivity. A ceramic layer with electrolyte is preferably used
with an SSE having lower ionic conductivity like a polymeric
SSE.
[0146] The binder and particles of the ceramic layer are discussed
in further detail below.
[0147] The polymeric binder comprises, consists of, or consists
essentially of at least one of a polymeric, oligomeric, or
elastomeric material and the same are not so limited. Any
polymeric, oligomeric, or elastomeric material not inconsistent
with this disclosure may be used. The binder may be ionically
conductive, semi-conductive, or non-conductive. Any gel-forming
polymer suggested for use in lithium polymer batteries or in solid
electrolyte batteries may be used. For example, the polymeric
binder may comprise at least one, or two, or three, etc. selected
from a polylactam polymer, polyvinyl alcohol (PVA), Polyacrylic
acid (PAA), Polyvinyl acetate (PVAc), carboxymethyl cellulose
(CMC), an isobutylene polymer, an acrylic resin, latex, an aramid,
or any combination of these materials. In some preferred
embodiments, the polymeric binder comprises, consists of, or
consists essentially of a polylactam polymer, which is a
homopolymer, co-polymer, block polymer, or block co-polymer derived
from a lactam. In some embodiments, the polymeric material
comprises a homopolymer, co-polymer, block polymer, or block
co-polymer according to Formula (1):
##STR00001##
[0148] wherein R.sub.1, R.sub.2, R.sub.3, and R.sub.4 can be alkyl
or aromatic substituents and R.sub.5 can be an alkyl substituent,
an aryl substituent, or a substituent comprising a fused ring; and
wherein the preferred polylactam can be a homopolymer or a
co-polymer where co-polymeric group X can be derived from a vinyl,
a substituted or un-substituted alkyl vinyl, a vinyl alcohol, vinyl
acetate, an acrylic acid, an alkyl acrylate, an acrylonitrile, a
maleic anhydride, a maleic imide, a styrene, a polyvinylpyrrolidone
(PVP), a polyvinylvalerolactam, a polyvinylcaprolactam (PVCap),
polyamide, or a polyimide; wherein m can be an integer between 1
and 10, preferably between 2 and 4, and wherein the ratio of 1 to n
is such that 0.ltoreq.:n.ltoreq.10 or 0.ltoreq.1:n.ltoreq.1. In
some preferred embodiments, the homopolymer, co-polymer, block
polymer, or block co-polymer derived from a lactam is at least one,
at least two, or at least three, selected from the group consisting
of polyvinylpyrrolidone (PVP), polyvinylcaprolactam (PVCap), and
polyvinyl-valerolactam.
[0149] In a preferred embodiment, a co-polymer block co-polymer
derived from a lactam comprises, in its backbone, a group capable
of creating cross-linking between at least two co-polymers or block
co-polymers chains. For example, the group may be an epoxide group
or an alkyl amine. When the group capable of creating cross-linking
between at least two co-polymers or block co-polymers chains is an
epoxide, the epoxide undergoes an epoxidation reaction to create
the cross-linking. In some embodiments, addition of a catalyst is
required. For example, if the group capable of creating
cross-linking between at least two co-polymers or block co-polymers
chains is an epoxide, catalyst comprising an alkyl amine group may
be added, and if the group is an alkyl amine, a catalyst comprising
an epoxide group may be added. A co-polymer or block-copolymer
described in this paragraph may have a structure as shown in FIG.
1) above, where X is a group capable of creating cross-linking
between at least two co-polymers or block co-polymers chains, e.g.,
an epoxide or alkyl amine-containing group. One embodiment of the
co-polymer block co-polymer derived from a lactam described in this
paragraph is shown below:
##STR00002##
[0150] An example of cross-linking between at least two co-polymers
or block co-polymers chains created by the co-polymer block
co-polymer derived from a lactam in above is shown in FIG. 11.
[0151] In the schematic representation directly above, the polymer
chains are PVP chains so R.sub.1, R.sub.2, R.sub.3, R.sub.4, and
R.sub.5 in the diagram directly above the above representation are
hydrogen and Y is 2. Use of a co-polymer or block co-polymer
derived from a lactam that comprises, in its backbone, a group
capable of creating cross-linking between at least two co-polymers
or block co-polymers chain can increase thermal stability, increase
electrolyte stability, improve wetting, and improve CV performance
of a resulting coating layer.
[0152] In another preferred embodiment, the polymeric binder
comprises, consists of, or consists essentially of polyvinyl
alcohol (PVA). Use of PVA may result in a low curl coating layer,
which helps the substrate to which is it applied stay stable and
flat, e.g., helps prevent the substrate from curling. PVA may be
added in combination with any other polymeric, oligomeric, or
elastomeric material described herein, particularly if low curling
is desired.
[0153] In another preferred embodiment, the polymeric binder may
comprise, consist of, or consists essentially of an acrylic resin.
The type of acrylic resin is not particularly limited, and may be
any acrylic resin that would not be contrary to the goals stated
herein, e.g., providing a new and improved coating composition that
may, for example, be used to make battery separators having
improved safety. For example, the acrylic resin may be at least
one, or two, or three, or four selected from the group consisting
of polyacrylic acid (PAA), polymethylmethacrylate (PMMA),
polyacrylonitrile (PAN), and polymethyl acrylate (PMA).
[0154] In other preferred embodiments, the polymeric binder may
comprise, consist of, or consist essentially of carboxymethyl
cellulose (CMC), an isobutylene polymer, latex, or any combination
these. These may be added alone or together with any other suitable
oligomeric, polymeric, or elastomeric material.
[0155] In some embodiments, the polymeric binder may comprise a
solvent that is water only, an aqueous or water-based solvent, or a
non-aqueous solvent. When the solvent is water, in some
embodiments, no other solvent is present. The aqueous or
water-based solvent may comprise a majority (more than 50%) water,
more than 60% water, more than 70% water, more than 80% water, more
than 90% water, more than 95% water, or more than 99%, but less
than 100% water. The aqueous or water-based solvent may comprise,
in addition to water, a polar or non-polar organic solvent. The
non-aqueous solvent is not limited and may be any polar or
non-polar organic solvent compatible with the goals expressed in
this application. In some embodiments, the polymeric binder
comprises only trace amounts of solvent, and in other embodiments
it comprises 50% or more solvent, sometimes 60% or more, sometimes
70% or more, sometimes 80% or more, etc.
[0156] The ratio of heat-resistant particles to polymeric binder in
the coating composition is, in some embodiments, 50:50 to 99:1, in
other embodiments, it is 70:30 to 99:1 or 90:10 to 98:2, and in
further embodiments, it is 90:10 to 99:1. This ratio affects
coverage of the heat-resistant particles by the polymeric binder.
For example, when the ratio of heat-resistant particles to
polymeric binder is lower, there will be more coverage of the
heat-resistant particles with binder (e.g., as shown on the right
below), and with the ratio of heat-resistant particles to polymeric
binder is higher, there will be less coverage of the heat-resistant
particles, e.g., as shown on the left in FIG. 7).
[0157] In a preferred embodiment, at least one of the
heat-resistant particles is coated or partially-coated by the
polymeric binder. For example, in some embodiments, 0.01 to 99.99%
of the surface area of at least one of the heat-resistant particles
(or of the surface area of all of the heat-resistant particles) is
coated by the binder. In some embodiments, 0.01 to 99.99% of the
total surface area of the heat-resistant particles in the
composition is coated with polymeric binder.
[0158] In another aspect, heat-resistant particles are added to the
coating composition described herein. The size, shape, chemical
composition, etc. of these heat-resistant particles is not so
limited. The heat-resistant particles may comprise an organic
material, an inorganic material, e.g., a ceramic material, or a
composite material that comprises both an inorganic and an organic
material, two or more organic materials, and/or two or more
inorganic materials.
[0159] In some embodiments, heat-resistant means that the material
that the particles are made up of, which may include a composite
material made up of two or more different materials, does not
undergo substantial physical changes, e.g., deformation, at
temperatures of 200.degree. C. Exemplary materials include aluminum
oxide (Al.sub.2O.sub.3), silicon dioxide (SiO.sub.2), graphite,
etc. Non-limiting examples of inorganic materials that may be used
to form the heat-resistant particles disclosed herein are as
follows: iron oxides silicon dioxide (SiO.sub.2), aluminum oxide
(Al.sub.2O.sub.3), boehmite (Al(O)OH), zirconium dioxide
(ZrO.sub.2), titanium dioxide (TiO.sub.2), barium sulfate
(BaSO.sub.4), barium titanium oxide (BaTiO.sub.3), aluminum
nitride, silicon nitride, calcium fluoride, barium fluoride,
zeolite, apatite, kaoline, mullite, spinel, olivine, mica, tin
dioxide (SnO.sub.2), indium tin oxide, oxides of transition metals,
and any combinations thereof.
[0160] Non-limiting examples of organic materials that may be used
to form the heat-resistant particles disclosed herein are as
follows: a polyimide resin, a melamine resin, a phenol resin, a
polymethyl methacrylate (PMMA) resin, a polystyrene resin, a
polydivinylbenzene (PDVB) resin, carbon black, graphite, and any
combination thereof.
[0161] The heat-resistant particles may be round, irregularly
shaped, flakes, etc. The average particle size of the
heat-resistant material ranges from 0,01 to 5 microns, from 0.03 to
3 microns. from 0.01 to 2 microns. etc.
[0162] As described above, in a preferred embodiment, at least one
of the heat-resistant particles added to the coating composition
described herein is coated or partially-coated by the polymeric
binder. In other embodiments, the heat-resistant particles may (in
addition to or as an alternative to being coated or
partially-coated by the polymeric binder) be coated or partially
coated by a compatibilizer, e.g., a material that makes the
particles more miscible with the polymeric binder. Generally, the
heat-resistant particles may be coated or uncoated in any way that
would not be inconsistent with the stated goals herein.
[0163] The coating composition comprises at least one, or two, or
three, etc. of (a) a cross-linker, (b) a low-temperature shutdown
agent, (c) an adhesion agent, (d) a thickener, (e) a friction
reducing agent, and (f) a high-temperature shutdown agent.
[0164] Cathode Interface Layer
[0165] The optionally provided cathode interface layer is not so
limited. Options for the optionally provided cathode interface
layer are the same as those for the anode interface layer and the
cathode interface layer may provide many of the same functions as
the anode interface layer, e.g., acting as a shock absorber and
improving ionic conductivity.
[0166] Like the anode interface layer, the cathode interface layer
may be formed on at least one of a surface of the cathode, a
surface of the SSE, or both a surface of the cathode and a surface
of the SSE. In some embodiments, the cathode interface layer is
formed directly on the surfaces and in other embodiments, there are
intervening layers formed in between the surface of the cathode or
SSE and the interface layer. Regardless of how the interface layer
is formed, in the final battery, the cathode interface layer is
always between the SSE and the cathode.
Hybrid Solid State Electrolyte
[0167] The inventive hybrid solid state electrolyte (HSSE) is not
so limited. The HSSE is as described herein. The HSSE may be
manufactured separately from the rest of the battery by providing
at least an anode interface layer on the surface of an SSE. The
anode interface layer is as described herein. In some embodiments
that are preferred, the anode interface may be provided directly
onto a surface of the SSE, and in other embodiments, intervening
layers may be provided between the SSE and the anode interface
layer. One example of a possible intervening layer is an adhesive
layer.
[0168] Once assembled, the separately made and sold HSSE may be
placed in a battery, e.g., a battery as described herein, with the
anode interface facing towards the anode and the cathode interface
layer facing toward the cathode. In some embodiments, a cathode
interface layer and an anode interface layer may also be applied to
a surface of the cathode and the anode, respectively. Use of the
same material to form the layer on the anode and cathode as is used
for the anode and cathode material of the HSSE may improve adhesion
between the anode and the HSSE and the cathode and the HSSE.
Vehicle, Storage System, or Device
[0169] The batteries and HSSEs described herein may be included in
any battery mudule or pack, vehicle, storage system, or device,
including electric cars, trucks, motorcycles, scooters, etc. Use of
these batteries and HSSEs is not limited.
Method of Making an HSSE
[0170] The method for forming an HSSE as described herein are not
so limited. In some embodiments, the method may comprise, consist
of, or consist essentially of forming an anode interface layer on a
surface of an SSE. The anode interface layer and the SSE are not so
limited and may be any SSE or anode interface layer as described
herein. In some preferred embodiments, the anode interface layer is
formed directly on a surface of the SSE, i.e., with no intervening
layers formed in between. In other embodiments, the method may
comprise a step of forming an intervening layer between the SSE and
the anode interface layer.
[0171] In other preferred embodiments, a cathode interface layer is
also formed on a surface of the SSE. The cathode interface layer is
not so limited and may be any cathode interface layer described
herein. The anode interface and the cathode interface layers may be
formed in any order on the SSE. The anode and the cathode interface
layers are formed on opposite surfaces of the SSE, so if the anode
interface layer is formed first, the cathode interface layer is
formed on an opposite side. If the cathode interface layer is
formed first, then the anode interface layer is formed on an
opposite side. In some preferred embodiments, the cathode interface
layer is formed directly on a surface of the SSE, but in other
embodiments, an intervening layer may be formed between the surface
of the SSE and the cathode interface layer.
[0172] The HSSE may be manufactured and sold to be used, for
example, in an improved solid-state battery. For example, it may be
used in the improved solid state battery described herein. In the
battery, the anode interface layer of the HSSE may face the anode
and the cathode interface layer may face the cathode.
[0173] The method for making the HSSE may include additional steps.
For example, additional steps to protect the HSSE when it is being
transported or stored before use.
Method of Making an Improved Solid State Battery
[0174] The method for forming an improved solid state battery is
not so limited. In some embodiments, the improved solid state
battery formed is an improved solid state battery as described
herein.
[0175] In some embodiments, the method for forming an improved
solid-state battery may comprise, consist of, or consist
essentially of, providing an anode, cathode, and SSE and then
forming an anode interface layer on at least one of a surface of
the anode, a surface of the SSE, or both a surface of the anode and
the SSE. In some preferred embodiments, the anode interface layer
is formed directly on the surface of the anode, the surface of the
SSE, or both the surface of the anode and the surface of the SSE.
In other embodiments, an intervening layer is formed between the
interface layer and the surface of at least one of the anode, the
SSE, or both the anode and the SSE.
[0176] In some embodiments, the method include a further step of
forming a cathode interface layer on at least one of the surface of
the cathode, the surface of the SSE, or both the surface of the
cathode and the surface of the SSE. In some preferred embodiments,
the cathode interface layer is formed directly on a surface of the
cathode, SSE, or both. In other embodiments, an intervening layer
is provided.
[0177] When a cathode interface layer is provided, the order of
forming the anode interface layer and the cathode interface layer
is not necessarily important. If the anode interface layer and the
cathode interface layer are both formed on the SSE, then they are
formed on opposite sides thereof. The only important thing is that
in the final battery the anode interface layer is formed between
the anode and the SSE and the cathode interface layer is formed
between the cathode and the SSE.
[0178] The method for forming a battery may comprise, consist of,
or consist essentially of any or all of the foregoing steps in
addition to any additional steps necessary to form a functioning
battery. A functioning battery is one that provides power for any
length of time.
Self-Healing SSE/In-Situ HSSE
[0179] In at least one embodiment, the glassy SSE may be a
self-healing SSE that includes LiI (as Li and I are included in
their ion form, L+, I-, in the glassy SSE). The I-will react with
the Li metal anode and form LiI at the surface. LiI is softer than
the SSE, electrically insulative, and ionically conductive. This
in-situ Lil forms an HSSE (Lil/SSE).
HSSE/Electrolyte Suppressing Technology/HSSE+Electrolyte
Suppressing Technology
[0179] [0180] The above described HSSE performance and improved SSE
Battery performance can be further improved by adding Electrolyte
Suppressing Technology (for example, electrolyte additives that
change V to 0.02) to further prevent dendrite formation.
[0181] Various embodiments of the present invention have been
described in fulfillment of the various objectives of the
invention. It should be recognized that these embodiments are
merely illustrative of the principles of the present invention.
Numerous modifications and adaptations thereof will be readily
apparent to those skilled in the art without departing from the
spirit and scope of the invention.
[0182] The present invention may be embodied in other forms without
departing from the spirit and the essential attributes thereof,
and, accordingly, reference should be made to the appended claims,
rather than to the foregoing specification, as indicating the scope
of the invention. Also contemplated are improved separators,
improved ceramic coatings, improved anodes, and the like.
* * * * *